Novel compositions based on reinforcement with microfibrillar networks of rigid-rod polymers

ABSTRACT

A process for fabricating a composite in the form of a network of microfibrils which includes interpenetrating the microfibrils with a matrix material to form a composite which includes two continuous interpenetrating phases, a matrix-material phase and a microfibrillar-reinforcing-network phase. There is disclosed composites in the form of a fiber and in the form of a film.

The present invention relates to processes for fabricating compositesand to composites formed in accordance with the processes.

Prior art, fiber-reinforced composites are fabricated by impregnation ofa yarn of fibers, which are typically on the order of ten micrometers indiameter, with a liquid matrix that is subsequently solidified to form asolid composite. The fiber-reinforced composite so formed is essentiallya two-phase material composed of a continuous matrix (e.g., epoxy) thatbinds the more rigid-fiber phase (e.g., glass or carbon). Thereinforcing-fiber phase may be either continuous or discontinuous.

An object of the present invention is to provide a new compositematerial in which the reinforcing phase is an interconnected network ofmicrofibrils of a rigid-chain polymer. As used, the term rigid polymerdenotes a polymer which has the ability to form a liquid crystallinephase, either in a solution or melt. The width of these microfibrils ison the order of 100 Å. Thus, the reinforcing phase in the compositematerial of the present invention differs from that of prior compositesby being an interconnected network and by having a typical width threeorders of magnitude smaller.

Another object is to utilize the rigid, oriented microfibrillar networkfor formation of composite fibers and films of enhanced strengthcharacteristics in shear, compression and tension, by judiciouscombination of microfibril-forming material and matrix material.

A further object is to use the microfibrillar-network composite fibersor films to produce bulk structures of enhanced properties by bondingtogether the composite fibers or films; the microporous nature of themicrofibrillar-network-reinforcing phase allows the precursor of thematrix material, imbibing the microfibrillar network, to be used forbonding between adjacent fibers or films.

Further objects are addressed hereinafter.

The foregoing objects are achieved, generally, in a process forfabricating a composite that includes forming a network of microfibrilsof a rigid polymer; and interpenetrating the microfibrils with a matrixmaterial to form a composite that includes two continuous andinterpenetrating phases, a matrix-material phase and amicrofibrillar-network-reinforcing phase. The objects are achieved alsoin a film formed in accordance with the foregoing process, a mat formedby weaving or otherwise combining many composites, and a multilayercomposite that includes a plurality of the composites, films or matsstacked in layers, one on the other and then solidified so that thematrix material bonds together the films to form a multilayeredcomposite structure.

The invention is hereinafter described with reference to theaccompanying drawing in which:

FIG. 1A is greatly enlarged a longitudinal view of a diagrammaticrepresentation of a fiber in the form of an oriented network or mesh ofmicrofibrils with a coagulant (e.g., water) within the network ofmicrofibrils;

FIG. 1B shows a greatly enlarged view of the region designated 10 inFIG. 1A;

FIG. 1C shows the fiber of FIG. 1A after drying to remove the coagulantwithin the mesh;

FIG. 2 is an electron micrograph of a longitudinal view of a fiber likethe fiber in FIG. 1A except with the coagulant within the mesh replacedby a matrix material in accordance with the present teaching;

FIG. 3 is an isometric view of a multilayered composite formed offibers, like the fiber in FIG. 2, into a film and then formed inmultilayers of the film;

FIG. 4 is a schematic of dry-jet/wet-spinning apparatus operable to formthe oriented network of microfibrils shown in FIG. 1A;

FIG. 5 shows the tensile force-strain behavior of coagulated fibers ofthe type shown in FIG. 1A (curve WC) and the type in FIG. 1C (curve AS);and

FIG. 6 is a stress-strain curve for a composite fiber as shown in FIG.2.

The fiber labeled 1 in FIG. 2 is a composite fabricated in accordancewith the present teachings. It includes a network of interconnectedmicrofibrils (see the network labeled 2 in FIG. 1B) in which themicrofibrils labeled 3 in FIG. 1B are oriented generally along the longaxis of the fiber and constitute one continuousmicrofibrillar-network-reinforcing phase of the composite 1 in FIG. 2.The other phase of the composite, as explained in some detail laterherein, is a matrix material which, in the composite fiber, is amaterial that serves to transmit shear forces, compression forces andtension forces between the microfibrils 3. In the final product, thematrix material fills the gaps (i.e., the spaces between themicrofibrils 3) labeled 4 in FIG. 1B, but, as later noted, at the stateof the network in FIGS. 1A and 1B the gaps 4 are filled with a coagulant(e.g., water). The dark parts in FIG. 2 (which is an electronmicrograph) are the microfibrils 3 and the light parts consist of thematrix material. For example, the microfibrillar network 2 can be formedin apparatus like the system in FIG. 4 during the dry-jet-wet spinningof solutions of poly(p-phenylene benzobisthiazole) which is called PBT.The coagulation (i.e., phase separation) of lyotropic liquid crystallinepolymers from solution under certain conditions yields 50-100 Å diametermicrofibrils of the rigid-chain polymer which forms a three-dimensionalnetwork of the microfibrils with surprisingly high mechanical integrity.The present invention utilizes the microfibrillar network formed byrigid-chain polymers in a composite that effectively utilizes thestrength and stiffness of the microfibrils and enhances thosecharacteristics.

The phase separation of rigid-chain polymers from solution intomicrofibrils is discussed, for example, in: W. G. Miller et al., in J.Polym. Sci., Polym. Symp., 65, 91 (1978); K. Tohyama et al., Nature,289, 813 (1981), and elsewhere.

One system for producing a network of microfibrils is thedry-jet/wet-spinning system labeled 20 in FIG. 4 for PBT or othermaterials. The polymer chain axis in the fiber or film thus formed isoriented parallel to the long axis of the microfibrils, as shown in FIG.1B.

The polymer from which the network is formed is first in the form of apolymer solution, as above indicated, within an extrusion chamber 6 fromwhich it is emitted through a spinnerette 7 as a highly viscous ribbon(or film) or fiber 5 which is formed between the spinnerette and acoagulation (e.g., water) bath 8. Essentially what occurs in the system20 is that the viscous polymer solution at 5 is stretched before itenters the coagulation bath 8 where it takes the form shown in FIGS. 1Aand 1B. In that form the microfibrils are from 50-100 Å in diameter witha coagulant (e.g., water) between them. These water-filledmicrofibrillar networks exhibit significant tensile force at break asindicated by the lower curve labeled WC in FIG. 5. The upper curve,labeled AS, is that of the dried material, and the relative strengthsare not significantly different from one another. (It should be noted atthis juncture that the resulting product can be a fiber typically aboutten micrometers in diameter or it can be a film about ten micrometersthick but much wider, depending upon the geometry of the die throughwhich the viscous ribbon or fiber 5 is emitted.)

The swollen fiber/film in the bath 8 passes around take-up rolls 9 and11 and is wound around a roll 12, but can pass around the roll 12 to afurther wrapping roll (not shown). According to the present teaching,the fiber/film within the bath (which is numbered 13 for presentpurposes) is that which is used; that is, the microfibrillar mesh is notdried (as shown in FIG. 1C) but is, rather, treated while in the wetstate, as depicted by the diagrammatic representation of FIG. 1B.

The object of this stage of the process is to introduce thematrix-forming material into the microfibrillar network formed asdescribed before. This can be achieved by collecting the microfibrillarmesh 13 on the roll 11 which can take up the fiber or film for furthertreatment. Irrespective of how the mesh 13 is collected, it is subjectedto a process whereby a matrix-forming material is introduced by adiffusion process of the matrix material or its precursor. If thematrix-forming molecules are soluble in the coagulant (e.g., water),they can be added in increasing concentration into the coagulant inwhich the microfibrillar mesh is immersed, or the collected mesh can beplaced in solutions of increasing concentration of matrix-formingmaterial, without allowing it to dry. Alternatively, the coagulant canbe gradually replaced by solvent in which the matrix-forming material issoluble, and which is miscible with the coagulant. This solvent is thengradually exchanged by the matrix-forming material as explained above.

After the matrix-forming material is infiltrated into the microfibrillarmesh, whether in the form of fiber or film, excess coagulant or solvent(if any) is dried. If the matrix-forming material is a reactive mixtureof organic material, it can be cured to form a solid matrix within theindividual fiber or film, thus forming amicrofibrillar-network-composite fiber or film.

Alternatively, the fibers and films impregnated with the matrix-formingmaterial may be laid out as desired, such as depicted in FIG. 3, andsubsequently solidified so that the matrix material also serves to bondthe individual microfibrillar-network-composite fibers or filmstogether.

By way of illustration, if the microfibrillar network used is made ofPBT, and the coagulant is water, the microfibrillar mesh is placed inalcohol-water mixtures of increasing alcohol content, without drying,until water is totally replaced by alcohol. It is then introduced intosolutions of an epoxy resin in alcohol with increasing epoxy resincontent. This resin includes all the components (epoxide, hardener andcatalyst) needed to form a suitable epoxy-matrix material upon curing.Then the microfibrillar network with the epoxy resin within it issuitably treated to solidify the matrix material.

As is noted above, in conventional composite fibers, the reinforcingfibers are typically about ten micrometers in diameter. In the presentmaterial, the composite fiber 1 in FIG. 2 is also about ten micrometersin diameter, but it is made up of microfibrils 3 (FIG. 1B) that areabout 50 to 100 Å in diameter, and these microfibrils are interconnectedto one another by microfibrillar interconnection; then they areconnected, as well, by the solid-matrix material which, as before noted,transmits forces among the microfibrils 3. The adhesion between fibrilsby virtue of the solidified-matrix material is about as strong ascohesion within the microfibrils. In addition to PBT, a number ofpolymers can be employed to produce the microfibrillar networks 3 asillustrated in the Table I below.

TABLE I Microfibril-Forming Materials--Rigid-Chain Polymers

1. Aromatic polyamides:

E.g.:

poly(p-benzamide) (PBA)

poly(p-phenyleneterephthalamide) (PPTA)

2. Polyhdrazides and polyamide-hydrazides

3. Aromatic-heterocyclic polymers

E.g.:

poly(p-phenylene benzobisthiazole) (PBT)

poly(p-phenylene benzobisoxazole) (PBO)

poly(p-phenylene benzobisimidazole) (PDIAB)

poly(2,5(6)benzothiazole) (AB-PBT)

poly(2,5(6)benzimidazole) (AB-PBI)

4. Poly isocyanates

5. Cellulose and its derivatives

cellulose

cellulose acetate

hydroxypropyl cellulose

6. Polyamino acids

poly(γ-benzyl-L-glutamate)

poly(ε-carbobenzoxy-L-Lysine)

poly(L-alanine)

and copolymers of the above

The coagulated PBT (or other fibers) 2 (i.e., formed of interconnectedmicrofibrils 3) can consist of as much as 95 percent coagulant. Thatcoagulant, as noted, can be first replaced by a compatible solutionwhich is replaced by the matrix material; or a compatible solution suchas water-soluble sodium silicate can be used when the coagulant iswater. Later, excess solvent or coagulant is dried off, and thecomposite is treated to render the matrix material solid.

The only requirement for impregnation of coagulated fibers (or films)with a matrix material is that the matrix material or matrix precursorreadily diffuse into the fibrillar network and replace the coagulant.Consequently, there are numerous organic and inorganic materials thatmay be selected as candidates for matrices to tailor the properties ofmicrofibrillar-network composites. Examples of potential matrixmaterials include: (1) thermosetting polymers that may be extended toother systems such as urethane and other low-viscosity reactants whichdiffuse into microfibrillar networks and replace coagulant, thecomposite being formed by polymerization and cross-linking afterimpregnation; (2) thermoplastic polymers wherein a thermoplastic matrixif formed by monomer impregnation, followed by polymerization (forexample, caprolactam may be substituted for coagulant and subsequentlypolymerized in situ to nylon-6) and (3) low-molecular weight materials,crystalline and amorphous organic and inorganic materials that areselected to form composites with unique compositions. Organic matrixescan be heat treated in situ to form a carbon matrix; ceramics andglasses can be introduced into the microfibrillar network from solution.For example, soluble silicates can be deposited in a microfibrillarnetwork to form a continuous glass-matrix phase; and low-melting solubleglass formulations can be used to allow fusion of the glass matrix afterdeposition from solution.

As indicated above, substances that form the basis for the matrixmaterial must be such that in solution such substances are able todiffuse into the microfibrillar network. These substances can becompatible with the coagulant so that a very concentrated solutionthereof will result in the matrix-forming substance diffusing into thereplacing most or all of the coagulant; or an intermediate step using acompatible solvent can be employed to remove the coagulant, thecompatible solvent then being replaced by a substance which forms thematrix material.

Example of matrix-forming materials are given below.

MATRIX MATERIALS

I. Organic materials which can be polymerized to form a cross-linkednetwork.

A. Epoxy resins

The infiltration mixture should include all the reaction components,i.e., epoxide, cross-linking agent and catalyst.

The epoxide can be of the following class: aromatic, aliphatic,cycloaliphatic.

The cross-linking agent can be either of the anhydride or amine type.

    __________________________________________________________________________    Examples:                                                                     Epoxide    Cross-linking Agent                                                                     Catalyst                                                                              Comments                                         __________________________________________________________________________    *Epon ® 828.sup.(1)                                                                  Boron triflouride-                                                                        --    aromatic                                                    mono-ethyl-amine                                                                        epoxide                                                             complex (BF.sub.3 MEA)                                             *ERL ® 4206.sup.(2)                                                                  nonenyl succinic                                                                        dimethyla-                                                                            eycloaliphatic                                   (Vinyl cyclo-        mino-ethanol                                                                          epoxide ("Spurr Resin")                          hexene dioxide)                                                               diglycidyl ether                                                                         dodecenyl succinic                                                                      2,4,6 tris-                                                                           aliphatic                                        of polypropylene                                                                         annhydride                                                                              (diamethyl-                                                                           epoxide                                          glycol DER ® 732.sup.(3)                                                                       amino-ethanol)                                           __________________________________________________________________________     *These formulations have been tested.                                         .sup.(1) Shell Chemical Corporation.                                          .sup.(2) Union Carbide Corporation.                                           .sup.(3) Dow Chemical Corporation.                                       

B. Phenolic resins

E.g., a novolac with hexamethylene tetramine.

C. Silicone resins

D. Polyimides

1. Polyamic-acid precursor (e.g., Skybond 703®, Monsanto).

2. Imide oligomers or bisimide monomers containing unsaturated aliphaticend groups.

E. Polyurethanes and polyureas

II. Monomers which can polymerize to a linear polymer.

A. Heterocyclic monomers

E.g.:

(1) ε-caprolactam (forming nylon 6)

(2) ε-caprolactone (forming polyester)

B. Vinyl monomers with suitable initiator

E.g., styrene, methyl methacrylate, acrylonitrile.

III. Polymers infiltrated after coagulation, or spun together insolution with the rigid-chain polymer in a common solvent.

polyamides (Nylon 6, Nylon 6,6)

polyesters

poly ether ketone (PEEK)

cellulose nitrate (lacquer)

IV. Inorganic materials.

A. Silicates sodium silicate, potassium silicate, and water solubleformulations of the above.

E.g.:

(1) Na₂ O: 3.3 SiO₂ (40° Be) .sup.(1)**

(2) Mixtures of (1) with metal oxides (such as zinc oxide, magnesiumoxide) which render the glass fusible at moderate temperature so that ahomogeneous interconnected glass matrix if formed

B. Silicon alkoxides

E.g., tetraethyl orthosilicate

The batch process referred to above can be employed, but a step-savingvariation of the fabrication of microfibrillar-network composites is tospin polymer fibers into a coagulation bath containing a matrixprecursor. This would eliminate the need for a diffusion controlledexchange of matrix for coagulant. Also, multiple loops of the fiber at13 can be employed with multiple chambers of concentrated-matrixmaterial.

A suitable matrix-forming material may also be dissolved together with arigid, microfibril-forming polymer, in a common solvent prior to theformation of a fiber or film such as in the spinning apparatus shown inFIG. 4. For example, a solution of PBT and nylon can be formed inmethane sulfonic acid at room temperature. The solution thus preparedcan be extruded to form fibers or films using an apparatus such as shownin FIG. 4. Upon coagulation, such as in a water bath (8 in FIG. 4), therigid polymer will form an interconnected microfibrillar network,interpenetrated with the matrix material if the ratio of the rigidpolymer to the matrix-forming material is high enough (e.g., above 1:3weight). The spaces between the interconnected microfibrils are filledwith both matrix material and coagulant. Removal of coagulant, as bydrying, retains an interconnected rigid microfibrillar network,interpenetrated with the matrix material.

Advantages that may be realized from use of microfibrillar networks asreinforcement for composite materials include among others: (1)tremendous increase in interfacial surface area (improvements inutilization of reinforcement properties, toughness and mechanical energyabsorption characteristics; furthermore, the network provides a tortuouspath for crack propagation to reduce the tendency to failcatastrophically); (2) reduction of residual stresses and voids in thereinforcement phase (collapse of the coagulated fiber or film withdrying is prevented by impregnation with a matrix); (3) because themicrofibrillar-network composite is composed of two interpenetratingphases, transfer of external loads to each phase does not require astrong interfacial bond (therefore, microfibrillar-network compositesmay be designed to allow each phase to contribute to different materialproperties such as, for example, the polymer network can provide tensilestrength while a ceramic or glassy matrix can provide compressivestrength to the composite); and (4) microscopic fibers of rigid-rodpolymers are composed of microfibrils which have been brought intocontact after coagulation via drying and, therefore, the properties ofsuch fibers can never equal those of the microfibrils. Unless theadhesion between microfibrils can be made as strong as the cohesionwithin microfibrils, the microfibrils will be the superior form of thepolymer for reinforcement.

Modifications of the invention herein disclosed will occur to personsskilled in the art and all such modifications are deemed to be withinthe scope of the invention as defined by the appended claims.

What is claimed is:
 1. A composite that comprises a network ofinterconnected microfibrils of rigid polymer chains that are orientedalong the long axis of the microfibrils and constitute one continuousmicrofibrillar-network-reinforcing phase of the composite, and asolid-matrix material interpenetrated within the three dimensionalnetwork and adhered to the microfibrils of the three dimensionalmicrofibrillar chains to constitute a second continuous phase, in whichthe matrix phase serves to transmit at least one of enhanced shearforces, compression forces and tension forces between the microfibrils.2. A composite according to claim 1 in which the matrix material istaken from the group consisting of cross-linkable organic materials. 3.A composite according to claim 1 in which the matrix material is aninorganic.
 4. A composite according to claim 1 in which the matrixmaterial is a glass.
 5. A composite according to claim 1 in which thematrix material is sodium silicate.
 6. A composite according to claim 1in which the composite is a fiber and in which the microfibrils areoriented along the long axis of the fiber and constitute one continuousmicrofibrillar-reinforcing phase of the fiber.
 7. A composite accordingto claim 1 in which the composite is formed in the form of a mat.
 8. Amultilayered composite that comprises a plurality of layer of the mat inclaim 7 formed one upon the other and cured, whereby the solid-matrixmaterial serves, upon curing, as a binder between layers.
 9. A compositeaccording to claim 8 in which individual microfibrils havecross-dimensions between about 50 Å and 100 Å, in which adhesion betweenthe microfibrils is about as strong as cohesion within the microfibrilsand in which the microfibrils are oriented along the long axis of thecomposite and constitute one continuousmicrofibrillar-network-reinforcing phase of the composite.
 10. Acomposite according to claim 1 in which the polymers that form themicrofibrils are taken from the groups consisting of aromaticpolyamides; polyhydrazides and polyamide-hydrazides;aromatic-heterocyclic polymers; poly isocyanates; cellulose and itsderivatives; polyamino acids and copolymers thereof.
 11. A compositeaccording to claim 10 in which the aromatic polamides are taken from thegroups consisting of poly(p-benzamide) (PBA) andpoly(p-phenyleneterephthalamide) (PPTA); the aromatic-heterocyclicpolymers are taken from the groups consisting of poly(p-phenylenebenzobisthiazole) (PBT), poly(p-phenylene benzobisoxazole) (PBO),poly(p-phenylene benzobisimidazole) (PDIAB), poly(2,5(6)benzothiazole)(AB-PBT), and poly(2,5(6)benzimidazole) (AB-PBI); the cellulose and itsderivatives is taken from the group consisting of cellulose, celluloseacetate, and hydroxypropyl cellulose; and the polyamino acids are takenfrom the group consisting of poly(γ-benzyl-L-glutamate),poly(ε-carbobenzoxy-L-Lysine), and poly(L-alanine).
 12. A compositeaccording to claim 1 is which the matrix materials are taken from thegroup consisting of: organic materials; monomers which can polymerize toa linear polymer; polymers which can infiltrate after coagulation or canbe spun together in solution with rigid-chain polymer in a commonsolvent; and an inorganic material.
 13. A composite according to claim 1in which adhesion between fibrils of the microfibrils by virtue of thesolid-matrix material is about as strong as cohesion between saidmicrofibrils.
 14. A composite according to claim 1 in which thecomposite is one that effectively utilizes the strength and stiffnesscharacteristics of the microfibrils and in which the solid-matrixmaterial enhances those characteristics.
 15. A composite according toclaim 1 in which the individual microfibrils have cross-dimensions nogreater than about 100 Å and the composite is a fiber about tenmicrometers in diameter.
 16. A composite according to claim 15 in whichthe individual microfibrils have cross-dimensions between 50 and 100 Å,in which adhesion between the microfibrils is about as strong ascohesion within the microfibrils and in which the microfibrils areoriented along the long axis of the composite and constitute onecontinuous three-dimensional microfibrillar-network-reinforcing phase ofthe composite.
 17. A composite according to claim 1 in which themicrofibrils of rigid polymer chains denote a polymer which has theability to form a liquid crystalline phase, either in solution or melt,the reinforcing phase in the composite material being an interconnectednetwork and having a typical width three orders of magnitude smallerthan other composites.
 18. A composite that comprises athree-dimensional network of many interconnected microfibrils, that is,the microfibrils are directly connected to other like microfibrils, ofrigid polymer chains that are oriented along the long axis of themicrofibrils and of the composite and constitute one continuousthree-dimensional microfibrillar-network-reinforcing phase of thecomposite, and a solid-matrix material interpenetrated within thethree-dimensional network and adhered to the microfibrils of themicrofibrillar chains to constitute a second continuous phase, in whichthe matrix phase serves to transmit at least one of enhanced shearforced, compression forces and tension forces between the microfibrilsof the composite.
 19. A composite according to claim 18 in which saidcomposite is a composite fiber.
 20. A composite according to claim 19 inwhich said fiber is of the order of ten micrometers in diameter.
 21. Acomposite according to claim 18 in which said composite is a compositefilm.
 22. A composite according to claim 21 in which the composite filmis the order of ten micrometers thick.